IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 Hemisynthesis, NMR Characterization and UHPLC-Q-Orbitrap /MS² identification of (+)-Catechin oxidation products in red wines and grape seed extracts

Hemisynthesis, NMR Characterization and UHPLC-Q-Orbitrap /MS² identification of (+)-Catechin oxidation products in red wines and grape seed extracts

Abstract

(+)-Catechin—laccase oxidation dimeric standards were hemi-synthesized using laccase from Trametes versicolor in a water-ethanol solution at pH 3.6. Eight fractions corresponding to eight potential oxidation dimeric products were detected. The fractions profiles were compared with profiles obtained with two other oxidoreductases: polyphenoloxidase extracted from grapes and laccase from Botrytis cinerea. The profiles were very similar, although some minor differences suggested possible dissimilarities in the reactivity of these enzymes. Five fractions were then isolated and analyzed by 1D and 2D NMR spectroscopy. The addition of traces of cadmium nitrate in the samples solubilized in acetone-d6 led to fully resolved NMR signals of phenolic protons, allowing the unambiguous structural determination of six reaction products, one of the fractions containing two enantiomers. These products were then analyzed in grape seed extracts and red wines (UHPLC-Q-Orbitrap MS). The different dimers had different fragmentation patterns according to their interflavan linkage position. Oxidation dimeric compounds had a specific fragment ion at m/z 393, missing for B-Type dimers fragmentations. A fragment ion at m/z 291 occurred and was specific for oxidation dimeric compounds with a C-O-C linkage. Higher level oxidation products had abundant specific fragments: m/z 425, 397 and 245. These fragmentations were useful to identify them in complex samples such as grape seed extracts and wines. Three grape varieties and three ripening stages were selected and the corresponding seed extracts were obtained. The analyses revealed an increasing trend for the oxidation markers during grape ripening. The analysis of Syrah wines (2018, 2014, 2010) showed a decreasing trend of these molecules during wine ageing which might be due to further oxidation.

DOI:

Publication date: June 23, 2022

Issue: IVAS 2022

Type: Article

Authors

Saucier Cedric1, Deshaies Stacy1, Le Guernevé Christine1,2, Sommerer Nicolas1,2, Garcia Lucas Suc François1, Mouls Laetitia1

1SPO, Université de Montpellier, INRAE, Institut Agro, UMR SPO, Faculté de Pharmacie, 15 avenue Charles Flahault, 34000 Montpellier, France
2INRAE, PROBE Research Infrastructure, PFP Polyphenol Facility, 34060 Montpellier, France

Contact the author

Keywords

wine, grape, polyphenol,oxidation, catechin

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

Photoselective shade films affect grapevine berry secondary metabolism and wine composition

Grapevine physiology and production are challenged by forecasted increases in temperature and water deficits. Within this scenario, photoselective overhead shade films are promising tools in warm viticulture areas to overcome climate change related factors. The aim of this study was to evaluate the vulnerability of ‘Cabernet Sauvignon’ grape berry to solar radiation overexposure and optimize shade film use for berry integrity. A randomized complete block design field study was conducted across two years (2020-2021) in Oakville, Napa Valley, CA, with four shade films (D1, D3, D4, D5) differing in the percent of radiation spectra transmitted and compared to an uncovered control (C0). Integrals for gas exchange parameters and mid-day stem water potential were unaffected by the shade films in 2020 and 2021. By harvest, berries from uncovered and shaded vines did not differ in their size or primary metabolism in either year. Despite precipitation exclusion during the dormant season in the shaded treatments, yield did not differ between them and the control in either season. In 2020, total skin anthocyanins (mg/g fresh mass) in the shaded treatments was greater than C0 during berry ripening and at harvest. Conversely, flavonol concentrations in 2020 were reduced in shaded vines compared to C0. The 2020 growing season highlighted the impact of heat degradation on flavonoids. Flavonoid concentrations in 2021 increased until harvest while flavonoid degradation was apparent from veraison to harvest in 2020 across shaded and control vines. Wine analyses highlighted the importance of light spectra to modify wine composition. Wine color intensity, tonality and anthocyanin values were enhanced in D4 whereas antioxidant properties were enhanced in C0 and D5 wines. Altogether, our results highlighted the need of new approaches in warm viticulture areas given the impact that composition of light has on berry and wine quality.

Is wine terroir a valid concept under a changing climate?

The OIV[i] defines terroir as a concept referring to an area in which collective knowledge of the interactions between the physical and biological environment (soil, topography, climate, landscape characteristics and biodiversity features) and vitivinicultural practices develops, providing distinctive wine characteristics. Those are perceptible in the taste of wine, which drives consumer preference and, therefore, wine’s value in the marketplace. Geographical indications (GI) are recognized regulatory constructs formalizing and protecting the nexus between wine taste and the terroir generating it. Despite considering updates, GIs do not consider the nexus as a dynamic one and do not anticipate change, namely of climate. Being climate a fundamental feature of terroir, it strongly impacts wine characteristics, such as taste. According to IPCC[ii], many widespread, rapid and unprecedented changes of climate occurred, some being irreversible over hundreds to thousands of years. Climatic shifts and atmospheric-driven extreme events have been widely reported worldwide. Recent climatic trends are projected to strengthen in upcoming decades, whereas extremes are expected to increase in frequency and intensity, forcing wines away from GI definitions. Geographical shifts of viticultural suitability are projected, often moving into regions and countries different from current ones. Some authors propose adaptation in viticulture, winemaking and product innovation. We show evidence of climate changing wine characteristics in the Douro valley, home of 270-year-old Port GI. We discuss herein resist or adapt stances for when climate changes the nexus between terroir and wine characteristics. Using the MED-GOLD[iii] dashboard, a tool allowing for easy visual navigation of past and future climates, we demonstrate how policymakers can identify future moments, throughout the 21st century under different emission scenarios, when GI specifications will likely need updates (e.g., boundaries, varieties) to reduce climate-change impacts.

Modelling vine water stress during a critical period and potential yield reduction rate in European wine regions: a retrospective analysis

Most European vineyards are managed under rainfed conditions, where seasonal water deficit has become increasingly important. The flowering-veraison phenophase represents an important period for vine response to water stress, which is seldomly thoroughly evaluated. Therefore, we aim to quantify the flowering-veraison water stress levels using Crop Water Stress Indicator (CWSI) over 1986–2015 for important European wine regions, and to assess the respective potential Yield Lose Rate (YLR). Additionally, we also investigate whether an advanced flowering-veraison phase may help alleviating the water stress with improved yield. A process-based grapevine model STICS is employed, which has been extensively calibrated for flowering and veraison stages using observed data at 38 locations with 10 different grapevine varieties. Subsequently, the model is being implemented at the regional level, considering site-specific calibration results and gridded climate and soil datasets. The findings suggest wine regions with stronger flowering-veraison CWSI tend to have higher potential YLR. However, contrasting patterns are found between wine regions in France-Germany-Luxembourg and Italy-Portugal-Spain. The former tends to have slight-to-moderate drought conditions (CWSI<0.5) and a negligible-to-moderate YLR (<30%), whereas the latter possesses severe-to-extreme CWSI (>0.5) and substantial YLR (>40%). Wine regions prone to a high drought risk (CWSI>0.75) are also identified, which are concentrated in southern Mediterranean Europe. An advanced flowering-veraison phase may have benefited from cooler temperatures and a higher fraction of spring precipitation in wine regions of Italy-Portugal-Spain, resulting in alleviated CWSI and moderate reductions of YLR. For those of France-Germany-Luxembourg, this can have reduced flowering-veraison precipitation, but prevalent alleviations of YLR are also found, possibly because of shifted phase towards a cooler growing season with reduced evaporative demands. Overall, such a retrospective analysis might provide new insights towards better management of seasonal water deficit for conventionally vulnerable Mediterranean wine regions, but also for relatively cooler and wetter Central European regions.

Differential responses of red and white grape cultivars trained to a single trellis system – the VSP

Commercial grape production relies on training grapevine cultivars onto a variety of trellis systems. Training allows for well-lit leaves and clusters, maximizing fruit quality in addition to facilitating cultivation, harvesting, and diseases control. Although grapevines can be trained onto an infinite variety of trellis systems, most red and white cultivars are trained to the standard VSP (Vertical Shoot Positioning) system. However, red and white cultivars respond differently to VSP in fruit composition and growth characteristics, which are yet to be fully understood. Therefore, the objective of this study was to examine the influence of the VSP trellis system on fruit composition of three red, Cabernet Sauvignon, Merlot and Syrah, and three white, Chardonnay, Riesling, and Gewurztraminer cultivars grown under uniform growing conditions in the same vineyard. All cultivars were monitored for maturity and harvested at their physiologically maximum possible sugar concentration to compare various fruit quality attributes such as Brix, pH, TA, malic and tartaric acids, glucose and fructose, potassium, YAN, and phenolic compounds including total anthocyanins, anthocyanin profile, and tannins. A distinct pattern in fruit composition was observed in each cultivar. In regards to growth characteristics, Syrah grew vigorously with the highest cluster weight. Although all cultivars developed pyriform seeds, the seed size and weight varied among all cultivars. Also varied were mesocarp cell viability, brush morphology, and cane structure. This knowledge of the canopy architectural characteristics assessed by the widely employed fruit compositional attributes and growth characteristics will aid the growers in better management of the vines in varied situations.

Elevational range shifts of mountain vineyards: Recent dynamics in response to a warming climate

Increasing temperatures worldwide are expected to cause a change in spatial distribution of plant species along elevational gradients and there are already observable shifts to higher elevations as a consequence of climate change for many species. Not only naturally growing plants, but also agricultural cultivations are subject to the effects of climate change, as the type of cultivation and the economic viability depends largely on the prevailing climatic conditions. A shift to higher elevations therefore represents a viable adaptation strategy to climate change, as higher elevations are characterized by lower temperatures. This is especially important in the case of viticulture because a certain wine-style can only be achieved under very specific climatic conditions. Although there are several studies investigating climatic suitability within winegrowing regions or longitudinal shifts of winegrowing areas, little is known about how fast vineyards move to higher elevations, which may represent a viable strategy for winegrowers to maintain growing conditions and thus wine-style, despite the effects of climate change. We therefore investigated the change in the spatial distribution of vineyards along an elevational gradient over the past 20 years in the mountainous wine-growing region of Alto Adige (Italy). A dataset containing information about location and planting year of more than 26000 vineyard parcels and 30 varieties was used to perform this analysis. Preliminary results suggest that there has been a shift to higher elevations for vineyards in general (from formerly 700m to currently 850 m a.s.l., with extreme sites reaching 1200 m a.s.l.), but also that this development has not been uniform across different varieties and products (i.e. vitis vinifera vs hybrid varieties and still vssparkling wines). This is important for climate change adaptation as well as for rural development. Mountain areas, especially at mid to high elevations, are often characterized by severe land abandonment which can be avoided to some degree if economically viable and sustainable land management strategies are available.